Difluorocarbene free radicals in the synthesis of fluorinated olefinic compounds



April 11, 1961 A. ERREDE ETAL 2,979,539 DIFLUOROCARBENE FREE RADICALS IN THE SYNTHESIS Filed Jan. 6, 1959 F/ci.

0F' FLUORINATED OLEFINIC COMPOUNDS 3 Sheets-Sheet 1 A10/YEL) /NVf/vas ,5 0015/4. 59,950.5 Muff/4310575250 April 11, 1961 L. A. ERREDE ETAL 2,979,539 DIFLUOROCARBENE FREE RADIcALs IN THE SYNTHESIS 0F FLUORINATED OLEFINIC COMPOUNDS 3 Sheets-Sheet 2 Filed Jan. 6, 1959 @A f m l SN Alh SRQIJ W QN W d M w V/A 0 z QW EW uGRQQ SQ uS .EER

R @E b NER# W d w M QN VWA Z MEQ April l1, 1961 L. A. ERREDE ET AL DIELUoRocARBENE FREE RADICALS 1N THE SYNTHESIS 0F FLUORINATED oLEEINIc COMPOUNDS Filed Jan. 6, 1959 F/Cij 20A/5 l I cw wn N MM Z P0 7N w MN N Q k m USUQ c@ cf==ff2 l /l l l 2,979,539 u n nrFLUoRocARBENE FREE RADICALS IN'THE SYNTHESIS oF FLUoRlNATED oLEFINrc CoM- PoUNDs Louis A. Errede, St. Paul, and Wesley R. Peterson, North (laks, Minn., assignors to Minnesota Mining and Manufacturing Company, St. Paul, Minn., a corporation of Delaware Filed Jan. 6, 1959, SverrNo. 785,246 7 ciaims. (ci. 26o-653.3)

mers have found wide application where resistance to chemical and thermal attack are desired. Peruoropropene, for example, has been copolymerized with tetrauoroethylene to produce a high molecular' V weight interpolymer (U.S. 2,598,283). However, the methods generally employed for the preparation of uorinated Vethylenically unsaturatedcompounds with three or more carbon atoms have been costly and ineicient, particularly in high capacity production.

It is an object of this'invention to provide a method for the production of fluorinated, ethylenically unsaturated compounds in high yield.

It is another objectof this invention to provide an eicient process for the production of uorinated ethylenically unsaturated organic compounds with a minimum production of less desirable by-products.

Still another object of this invention is to provide a novel and commercially attractive method for the propropene. v

According to this invention, an ethylenically unsaturated compound is reacted with diuorocarbene radical to produce afluorinated ethylenically unsaturated organic compound having at least three carbon atoms per molecule. This reaction involves the addition of lthe v duction of fluorinated propenes, particularly perliuorofree radical :CP2 to an ethylenically unsaturated com# pound and can be conducted either with or without the presence of a catalyst or a Ydiluent. The reaction generally is believed to proceed as follows:

wherein X is hydrogen, fluorine or chlorine, and R is hydrogen, uorine, chlorine, or alkyl having no more` 2,979,539 Patented` Apr. 1 1, 1961.

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Y 2 fluoride, vinylidene chloride, vinyl chloride, 1,1-diuorodichlo'roethylene, propene, ethylene, 3,3,4,4,4pentauoro buetene-l, peruoropropene, and hexafluorobutene-l.

Generally the ethylenes are preferred particularly the fluorinated ethylenes. The use of tetrauoroethylene in this process, producing peruoropropene, constitutes a particularly preferred embodiment. It may also be desirable to use other perhalogenated ethylenes, such as triuorochloroethylene, as a reactant.

. Any method can be employed to produce the diuorocarbene radical, providing the free radical is available for the addition reaction. Such methods include the production of diuorocarbene during thepyrolysis of CHCIF2, as described in U.S. 2,551,573. It is also possible to obtain the diuorocarbene free radical during the pyrolysis of tetrauoroethylene at temperatures above 750 C. However, forl the purposes of this invention, the method of producing diuorocarbene is not critical.

Because of the relatively short life of the diuorocarbene free radical, it is essential that it and the ethylenically unsaturated compound be brought into contact during the period in which the free radical exists,'i.e., before the difluorocarbene radicals are consumed by selfcondensation, and at a temperature at which the addi-y tion reaction can proceed, usually above about 100 C.

The reaction can ba advantageously vperformed in a reaction tube similar to that appearing in Figure 1, although the process of this invention is not necessarily limited to a particular apparatus. Such tube is constructed of Monel, silver, alloy steel, or other material substantially inert to the reactants and reaction products and which will withstand the temperatures employed. Where the diliuorocarbene radical is produced by the pyrolysis of CFzHCl, the CFzHCl gas is introduced into one end of this tubular reactor and is heated therein to pyrolysis temperature as vit flows through a pyrolysis zone. Heat may be applied by electric coils or` other conventional heating means, and temperatures maybe measured by thermocouples located on the tube wall or -in the moving gas stream. A smaller tube inserted into the opposite end of the reactor tube and positioned coaxially therein introduces the ethylenically unsaturated organic compound into that section of the reaction zone in which diuorocarbene exists as a reactive free radical. The particular point of contact between the two reactants is determined experimentally and is related to the pyrolysis temperature, pressure, and residence time of the CFzHCl or diuorocarbene producing material. However, if the ethylenically unsaturated compound contacts the moving gas stream at a point upstream of the region in which difluorocarbene radical exists, it is subjected to pyrolysis temperatures which may, depending on such factors as residence time, etc., promote excessive pyrolysis of the Yethylenically unsaturated compound, and therebyY reduce 'the yield of the desired addition product.

Conversely, if the ethylenically unsaturated compound isintroduced into the moving gas stream at a point down- `stream of that regionpatuwhich the diuorocarbene radical exists, the addition-reaction cannot occur.

v`propene from CFgHCl Vand CFFCFz will be described l .that similar procedures can be employed with the other reactants described herein and with other operating conditions, within the scope of this disclosure.

It is to be understood' Figure 1 shows the temperature profile of a 1" I.D. Moncl reactor tube with the passage of one mole per minute flow of CFZHCl. The pyrolysis zone is heated to a temperature of about 700 C., selected in conjunc- 4 select the temperature and pyrolysis zone residence time of the tetrauoroethylene so as to prevent pyrolysis of the CF2=CF2. Figure 3 relates the mole concentration of the various components along the length of reactor tion with the pressure and CFzHCl residence time in tube, measured from the CFZHCl inlet end, with tetrathe pyrolysis zone so as to optimize production of diuomethylene introduction at the 91/2 point, uorocarbene radical. Generally, inthe case of mono- Figure 4 is a plot of the total mole concentration chlorodiiluoromethane, temperatures above about 600 a10ng the ylength of the reactor tube, C., and below about 1.000 C, may be used, the higher Figure 5 is a plot of total residence time and instantempefaufes tending t0 IICTCaSe PYrOlYSiS andV forma' 10 taneous residence time (average residence time in one tion of difluorocarbene at a given residence time in the inch intervals) as related to .the distance from the pyrolysis zone. Pressures may range between 0.01 and CFZHC] inlet end atmospheres absolute, but are preferably below 0.5 Figure 6 is a plot of the molar edneentration of the atmospheres for increased formation of reactive free recovered products as related to ,the blend point or point radicals FOY the Purposes -of the Preset iuustfatlon of introduction of the tetrauoroethylene. It will be a pressure of 130 mm. Hg or 0.171 atmospheres has been noted that the 91/2- 10" blend point region produces in emP10Yed Further data on the effe@ of tefperature this instance the optimum perfluoropropene with a miniand Pressure on pyrolysis of F2HCl 1S found m Indus' mum tetraluoroethylene residence .time in the pyrolysis trial and Engineering Chemlstry, v01. 39, NO- 3, PP- zone. This corresponds to a conversion of about 90%, 354-358- 20- based on HCl produced, and to a yield of 85/ 95 or about Figure 2 ls a Plot showmg the'prole f;the mQles 90% of perfluoropropene. The mixture leaving the reacof the various reactants and products'at various points tion tube is Washed with Water, cooled to about 70s along the reactor tube When no ethylemcuy unsaiufated C., and fractionally distilled to recoverthe desired prodcompound is introduced through the coax1ally positioned e not tube. The diuorocarbene radical concentration rises 25. Referring to the illustrative data appearing in the aforo to a maximum and then decreases as the radicals con mentioned figures, it is observed that the CFZHCI dense to fom CF2=CF2 Measurmg from the, efld of residence time in the pyrolysis zone is about 0.44 second the reactor mbe through Whch the CFZHCI 1s mug' and the CF2=CF2 residence timev in the pyrolysis zone is duced at a oW fate of 1 mole Per mmutf the PyrolySS about 0.05 second. Furthermore, pyrolysis of the latterl Zone extends generally 'from 5%" to 11 and the OPH' 30, does not -becorne important because of the short residence mum concentration of diuorocarbene free radlcal .exists time usually below about 0.5 second in the 91/2" to 12" Vange- The blend Pou or Pomt ,of As mentioned earlier, the process of this invention is introduction of the ethylenically unsaturated compound, not limited to the use of any one ethylenioauy unserm hereinafter used interchangeably with tetrafluoroethylene, rated monomer. Thus, a variety of compounds of com is coincident Withfhs optirimm anf appears at 91/2'." 3;.pounds can be produced by the reaction of dilluorocar- In Order to mmumze the resldence time of tile ethylem bene with ethylenically unsaturated olen, including the cally unsaturated monomer at the pyrolysls temperafollowing: ture, the operating conditions and physical dimensions of the pyrolysis zone are adjusted to place the point of optimum concentration of difluorocarbene radical at or 40 iCF2CR2=C12 CFaCF=CC12 and 1s01 1e1'S near the downstream end of the pyrolysis zone. tGPH-C172:CFCI. CF3 CF=CFC1 ano isomers When the rate of introduction of the tetrauoroethyl- ICF2+CF2=CH29 CF3 CF=CH2 and lsolnefs ene is 3 moles per minute, a 3:1 ratio of ethylenically TCFa'i-CHzzCHz) CF2HCH=CH2 and lsomefs unsaturated reactant to CFZHCI is provided. Generally, ICFZ+CH2=CHC1 CF2H CH=CHC1 and lsomefs an excess of the ethylenically unsaturated reactant, such aS CF2=CF2, io, above 121 m01@ Tati@ and UP i0 apelle Using the system earlier described, a series of runs were about 2011, iS desired S0 3S i0 Utilize more efeCUVeY made with chlorotrilluoroethylene as the ethylenically hE diuOI'OCal'beHe produced and t0 increase the unsaturated Ieactant The euent gases from the pyro- 0f addOIl Product aCCOIdIlgW The temperature 0f the lysis of CFzHCl were blended with chlorotrifluoroethyl- 'ethylenically unsaturated feaefanf, 65d-, CF2=CF2i Call 50 ene at distances from 2 to 4 inches downstream of the be varied over wide limits and should be suiciently low pyrolysis Zone, The liquid products were distilled to provide a quench effect (i-e., to lower the temperature through a 30" vacuum jacketed column with the still of the mixed reactant stream below the pyrolysis temhead held below 30 Q and Separated into two fracperature) and suiciently high to maintain the temperations: (1) B.P. below 20 C., and (2) B.P. above ture of the mixed reactant stream at a temperature at 55F-20" C. Analysis of the product boiling above -20 which addition will proceed, usually above about C., indicated a substantial yield of C3 or perfluoro- C., over the zone containing free difluorocarbene radicals chlorinated propene. The results of this series of runs (9i/z" to 14" in Figure 3). It is particularly essential to appear in Table I. v

TABLE I Temperature Dlstnce t Pyrglysls Pressure. Moles Mole Ratio' Moles (iglil Liltxslrldgilltin Run Pyrolysis Blend Zone mm. Hg CFiHCl Q FLL :CF: pro- :CF1 con- Zone, Point, From Feed CFzOFCl Produced ducedb verted to C. o. Blend CiFiolb Polnt,in.

1 77o 644 3.0 13o 1 1o 1/1 o 53 0.04 8 2 750 500 4.5 13o 1 69 1/3 o 69 0.05 7 3 74o 66o 4.o 123 1 97 1/3 o 73 0-14 1.9 4 728 716 2. 5 125 1 39 1/3 o 51 0.17 3a 5 722 710 2.o 13o 1 e9 1/3 o 79 0.17 s 772 738 2. 0 130 o 1/3; o (e) Ratio of N ilCFi=CFCl (2 moles CF2=CFCl feed). y D Minimum value, includes only CgFiCl in richest distilled fraction of product. o 5 grams of pyrolysis product (cyclobutanes. ete.). Y

Using the physical system described earlier (see Figure l), the following Table II illustrates particular exemplary operating conditions for still other iluorinated 6 Since many widely different embodiments of this invention may be made without departing from the spirit and scope thereof, it is to be understood that the specific embodiments herein are recited only for purposes of illusethylenically unsaturated reactants. 5 tration and are not to be construed as limiting.

TABLE II s pyrolysis Moles/mm. oversu Ethylenlcally Un- Moles/min ethylenic- Percent saturated Reactant CFHCI ally un- Blend Conversion T t, P, saturated T, C. of :CFg to sec. atm. reactant addition product CHP- CE2 0. 035 700 1.o 0.1 0.20 200 85 CF2=CC1 0. 03 700 0.8 0.3 0. 20 15o so CFsCFaCH=oH2 0.02 700 0.5 0.4 0.15 15o 74 Generally, the process of this invention involves the We claim:

reaction of diiuorocarbene free radical with an ethylenically unsaturated compound, preferably an ethylene compound. Because of the abbreviated life of such free radicals, it is an essential element of this process to bring the diuorocarbene -free radical into contact with the ethylenically unsaturated compound during the fbrief lifespan of the former, thereby to promote an addition reaction between the two and the formation of an ethylenically unsaturated compound having one more carbon atom than the original unsaturated reactant. For maximum yield, the residence time the ethylenically unsaturated reactant at pyrolysis temperatures is kept at a minimum and the temperatures of t-he reactants during the addition reaction (until the concentration of free radical approaches zero) is maintained above about 100 C., and under conditions at which substantially no pyrolysis of the unsaturated reactant occurs. objectionable pyrolysis of the ethylenically unsaturated reactant can readily |be ascertained under any given set of operating conditions by carrying out runs in the absence of the diuorocarbene radical and analyzing the resultant product. Only those conditions under which substantially no pyrolysis of the ethylenically unsaturated reactant occurs, i.e., less than about 5 percent pyrolysis of said reactant occurs, i.e., less than about 5 percent pyrolysis of said reactant, should be used, to avoid formation of saturated 'by-products and reduced yield of the desired addition product.

1. A process which comprises producing diiiuorocarbene free radical and reacting said diuorocarbene free radical lwith an ethylenically unsaturated compound having from 2 to 4 carbon atoms at a temperature above about C., and under conditions at which substantially no pyrolysis of `the ethylenically unsaturated compound occurs.

2. A process which comprises producing diuorocarbene free radicals and reacting said diiiuorocarbene free radical with a uorinated ethylene having only iiuorine, chlorine and hydrogen substituents at a temperature above albout 100 C., and under conditions at which substantially no pyrolysis of the iiuorinated ethylene occurs.

3. The process of claim 2 in which the iiuorinated ethylene is tetraiiuoroethylene.

4. The process of claim 2 in which the fluorinated ethylene is chlorotriuoroethylene.

5. The process of claim Z in which the iluorinated ethylene is v-inylidene iiuoride.

6. The process of claim 2 in which the fluorinated ethylene is dichlorodiiluoroethylene.

7. The process of claim 2 in Vwhich the temperature is atleast 500 C.

References Cited in the tile of this patent rUNITED STATES PATENTS 2,758,138 Nelson Aug. 7, 1956 

1. A PROCESS WHICH COMPRISES PRODUCING DIFULUOROCARBENE FREE DRADICAL AND REACTING SAID DIFLUROCARBENE FREE RADICAL SITH AN ETHYLENICALLY UNSATURATED COMPOUND HAVING FROM 2 TO 4 CARBON ATOMS AT A TEMPERATURE ABOVE ABOUT 100*C., AND UNDER CONDITIONS AT WHICH SUBSTANTIALLY NO PYROLIS OF THE ETHYLENICALLY UNSATURATED COMPOUND OCCURS. 